Diketopyrrolopyrrole polymers and small molecules

Patent metadata

Field	Value
Publication number	US-9293718-B2
Application number	US-201314386123-A
Country	US
Kind code	B2
Filing date	Apr 2, 2013
Priority date	Apr 4, 2012
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

The present invention relates to polymers, comprising a repeating unit of the formula (I), and compounds of formula (II), wherein Y, Y 15 , Y 16 and Y 17 are independently of each other a group of formula (a) characterized in that the polymers and compounds comprise silicon-containing solubilizing side chains and their use as organic semiconductor in organic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes.

First claim

The invention claimed is:

1. A polymer comprising a repeating unit of the formula

wherein
a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3;
R 1 and R 2 may be the same or different and are selected from the group consisting of a C 1 -C 100 alkyl group, which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ; and/or can optionally be interrupted by —O—, —S—, —NR 39 —, —COO—, —CO—, —OCO—, C 6 -C 24 arylene, C 2 -C 20 heteroarylene, C 3 -C 12 cycloalkylene, or D Si ,
a C 2 -C 100 alkenyl group, which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ; and/or can optionally be interrupted by —O—, —S—, —NR 39 —, —COO—, —CO—, —OCO—, C 6 -C 24 arylene, C 2 -C 20 heteroarylene, C 3 -C 12 cycloalkylene, or D Si ,
a C 3 -C 100 alkinyl group, which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ; and/or can optionally be interrupted by —O—, —S—, —NR 39 —, —COO—, —CO—, —OCO—, C 6 -C 24 arylene, C 2 -C 20 heteroarylene, C 3 -C 12 cycloalkylene, or D Si ,
a C 3 -C 12 cycloalkyl group, which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ; and/or can optionally be interrupted by —O—, —S—, —NR 39 —, —COO—, —CO—, —OCO—, C 6 -C 24 arylene, C 2 -C 20 heteroarylene, C 3 -C 12 cycloalkylene, or D Si ,
a C 6 -C 24 aryl group, which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ;
a C 2 -C 20 heteroaryl group, which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ; and
—CO—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl, —COO—C 1 -C 18 alkyl which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or E Si ; and/or can optionally be interrupted by —O—, —S—, —NR 39 —, —COO—, —CO—, —OCO—, C 6 -C 24 arylene, C 2 -C 20 heteroarylene, C 3 -C 12 cycloalkylene, or D Si ; wherein
E Si is —SiR 161 R 162 R 163 or —O—SiR 161 R 162 R 163 ,
D Si is —SiR 161 R 162 —, —SiR 161 R 162 —(O—SiR 161 R 162 ) d — or —O—SiR 161 R 162 —,
R 161 , R 162 and R 163 are independently of each other hydrogen, C 1 -C 25 alkyl, C 3 -C 12 cycloalkyl, which might optionally be substituted with C 1 -C 4 alkyl, C 1 -C 25 haloalkyl, C 2 -C 25 alkenyl, —O—SiR 164 R 165 R 166 , —(O—SiR 164 R 165 ) d —R 166 , C 1 -C 25 alkoxy, C 3 -C 24 (hetero)aryloxy, NR 167 R 168 , halogen, C 1 -C 25 acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C 1 -C 24 alkyl, halogen, cyano or C 1 -C 25 alkoxy;
R 164 , R 165 and R 166 are independently of each other hydrogen, C 1 -C 25 alkyl, C 3 -C 12 cycloalkyl, which might optionally be substituted with C 1 -C 4 alkyl, C 1 -C 25 haloalkyl, C 2 -C 25 alkenyl, —O—SiR 169 R 170 R 171 , —(O—SiR 169 R 170 ) d —R 171 , C 1 -C 25 alkoxy, C 3 -C 24 (hetero)aryloxy, NR 167 R 168 , halogen, C 1 -C 25 acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C 1 -C 24 alkyl, halogen, cyano or C 1 -C 25 alkoxy;
R 169 , R 170 and R 171 are independently of each other hydrogen, C 1 -C 25 alkyl, C 3 -C 12 cycloalkyl, which might optionally be substituted with C 1 -C 4 alkyl, C 1 -C 25 haloalkyl, C 2 -C 25 alkenyl, —O—Si(CH 3 ) 3 , C 1 -C 25 alkoxy, C 3 -C 24 (hetero)aryloxy, NR 167 R 168 , halogen, C 1 -C 25 acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C 1 -C 24 alkyl, halogen, cyano or C 1 -C 25 alkoxy;
R 167 and R 168 are independently of each other hydrogen, C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, or C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C 7 -C 25 arylalkyl;
d is an integer from 1 to 50;
R 39 is hydrogen, C 1 -C 18 alkyl, C 1 -C 18 haloalkyl, C 7 -C 25 arylalkyl, or C 1 -C 18 alkanoyl,
Ar 1 , Ar 1′ , Ar 2 , Ar 2′ , Ar 3 and Ar 3′ are independently of each other

wherein
X is —O—, —S—, —NR 8 —, —Si(R 11 )(R 11′ )—, —Ge(R 11 )(R 11′ )—, —C(R 7 )(R 7′ )—, —C(═O)—, —C(═CR 104 R 104′ )—,

R 3 and R 3′ are independently of each other hydrogen, halogen, E Si , halogenated C 1 -C 25 alkyl, cyano, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 arylalkyl, C 1 -C 25 alkyl substituted with one or more E Si , or C 1 -C 25 alkoxy;
R 4 , R 4′ , R 5 , R 5′ , R 6 , and R 6′ are independently of each other hydrogen, halogen, E Si , halogenated C 1 -C 25 alkyl, cyano, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 arylalkyl, C 1 -C 25 alkyl substituted with one or more E Si , or C 1 -C 25 alkoxy;
R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkyl substituted with one or more E Si , or C 7 -C 25 arylalkyl, or R 7 and R 7′ , or R 9 and R 9′ are together ═CR 104 R 104′ ;
R 8 and R 8′ are independently of each other hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 1 -C 25 alkyl substituted with one or more E Si , or C 7 -C 25 arylalkyl,
R 11 and R 11′ are independently of each other C 1 -C 25 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;
R 12 and R 12′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or —≡—R 13 , wherein R 13 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group;
Ar 1 , Ar 1′ , Ar 2 , Ar 2′ , Ar 3 and Ar 3′ are independently of each other

wherein
X 1′ is S, O, NR 107 —, —Si(R 117 )(R 117′ )—, —Ge(R 117 )(R 117′ )—, —C(R 108 )(R 109 )—, —C(═O)—, —C(═CR 104 R 104′ )—,

Assignees

• Basf Se

Inventors

• Hayoz Pascal

Classifications

• C09K2211/1491

  containing other combinations of heteroatoms · CPC title

• C09K2211/1466

  containing nitrogen as the only heteroatom · CPC title

• C09K2211/1458

  containing sulfur as the only heteroatom · CPC title

• C09K2211/1425

  Non-condensed systems · CPC title

• C09K2211/1416

  Condensed systems · CPC title